阅读说明：本技术 一种核燃料基体石墨粉、核燃料石墨基体材料及制备方法 (Nuclear fuel matrix graphite powder, nuclear fuel graphite matrix material and preparation method ) 是由 卢振明 刘兵 张�杰 周湘文 李江华 王磊 唐亚平 于 2020-04-09 设计创作，主要内容包括：本发明实施例涉及一种核燃料基体石墨粉、核燃料石墨基体材料及制备方法。本发明提供的核燃料基体石墨粉的制备方法包括下述步骤：将天然石墨粉、人造石墨粉、固态粘结剂混合；加入融合设备中处理；所述融合设备用于给粉体提供压应力和剪切力,将粘结剂包覆在石墨粉表面。本发明首次在本领域使用机械融合的方法来制备基体石墨粉,其以天然石墨粉、人造石墨粉和固态粘结剂为原料,为干法工艺,打破了本领域基体石墨粉仅有湿法制备工艺的现状,无需引入溶剂,并将单批次制备时间从现有湿法工艺的30-50h缩短至了1-2h,能耗仅为现有湿法工艺的1/40-1/20；且能获得与传统湿法工艺类似的包覆效果；所用设备更为简化；有效降低了生产成本,经济效益和社会效益高。(The embodiment of the invention relates to nuclear fuel matrix graphite powder, a nuclear fuel graphite matrix material and a preparation method thereof. The preparation method of the nuclear fuel matrix graphite powder provided by the invention comprises the following steps: mixing natural graphite powder, artificial stone ink powder and a solid adhesive; adding the mixture into fusion equipment for treatment; the fusion equipment is used for providing compressive stress and shearing force for the powder, and the binder is coated on the surface of the graphite powder. The method uses the mechanical fusion method to prepare the matrix graphite powder for the first time in the field, uses the natural graphite powder, the artificial stone toner and the solid binder as raw materials, is a dry process, breaks through the current situation that the matrix graphite powder only has a wet preparation process in the field, does not need to introduce a solvent, shortens the single-batch preparation time from 30-50h of the existing wet process to 1-2h, and has energy consumption only 1/40-1/20 of the existing wet process; and can obtain the similar cladding effect of the traditional wet process; the used equipment is more simplified; effectively reduces the production cost and has high economic benefit and social benefit.)

1. A method of preparing a nuclear fuel matrix graphite powder, the method comprising the steps of:

mixing natural graphite powder, artificial stone ink powder and a solid adhesive; adding the mixture into fusion equipment for treatment; the fusion equipment is used for providing compressive stress and shearing force for the powder, and the binder is coated on the surface of the graphite powder.

2. The method of claim 1, wherein: the fusion equipment comprises one or more of a mechanical fusion machine, a stirring ball mill or a planetary ball mill; optionally a mechanical fusion machine.

3. The production method according to claim 1 or 2, characterized in that: when the mixture is treated in the fusion equipment, the temperature in the container is 40-80 ℃, the relative rotating speed of the rotor and the cylinder is 2000-6000rpm, and the treatment time is more than or equal to 5 min.

4. The method of claim 1, wherein: the ratio of the graphite powder to the solid binder in the particle size D50 is more than or equal to 5: 1;

optionally, the natural graphite powder has a D50 of 20-60 μm; d50 of the artificial graphite powder is 25-70 μm; the D50 of the solid binder is less than or equal to 5 mu m.

5. The method of claim 1, wherein: the preparation method comprises the following steps: simultaneously adding natural graphite powder, artificial graphite powder and a solid binder into powder mixing equipment, and mixing; then adding the mixture into fusion equipment for treatment to obtain the composite material;

optionally, the mass ratio of the natural graphite powder to the artificial graphite powder is (2-8): 1, the mass ratio of the total weight of the natural graphite powder and the artificial graphite powder to the solid binder is (2-6): 1.

6. the method of claim 1, wherein: the preparation method comprises the following steps:

mixing natural graphite powder and a solid binder in powder mixing equipment, and adding the mixture into fusion equipment for treatment to obtain a first fusion; mixing artificial graphite powder and a solid binder in powder mixing equipment, and adding the mixture into fusion equipment for treatment to obtain a second fusion; adding the first fusion and the second fusion into a powder mixing device at the same time, and mixing to obtain the composite material;

optionally, the mass ratio of the natural graphite powder to the solid binder is (2-6): 1; the mass ratio of the artificial graphite powder to the solid binder is (2-6): 1; when the fusion powder is added into a powder mixing device, the mass ratio of the first fusion to the second fusion is (2-8): 1.

7. the method of claim 1, wherein: the natural graphite powder comprises one or more of natural crystalline flake graphite or natural microcrystalline graphite; optionally natural flake graphite;

and/or the artificial stone toner comprises one or more of graphite powder prepared by taking petroleum coke or pitch coke as a raw material;

and/or the solid binder comprises one or more of phenolic resin, cured furan resin, polyvinyl butyral, epoxy resin, polyurethane resin, carbonaceous solid pitch, mesophase pitch, or self-sintered mesophase carbon microspheres.

8. A nuclear fuel matrix graphite powder produced by the production method described in any one of claims 1 to 7.

9. A method of preparing a nuclear fuel graphite base material, the method comprising the steps of:

the nuclear fuel matrix graphite powder of claim 8 is subjected to pressing, carbonization and high-temperature purification to obtain a nuclear fuel graphite matrix material;

optionally, the pressing pressure is 200-; the carbonization is carried out under the protection of inert gas, and the carbonization temperature is 700-1100 ℃; the high-temperature purification temperature is 1600-2500 ℃.

10. A nuclear fuel graphite base material produced by the production method as set forth in claim 9.

Technical Field

The invention relates to the field of graphite materials for nuclear, in particular to nuclear fuel matrix graphite powder, a nuclear fuel graphite matrix material and a preparation method thereof.

Background

The graphite material has the advantages of high neutron moderating capacity, low neutron absorption cross section, good irradiation performance, low thermal expansion coefficient, high thermal conductivity, excellent mechanical property at high temperature and the like, and has mature processing and manufacturing technologies, and the properties determine the wide application of the graphite material in nuclear reactors. In addition to being used as a reactor structural material, many reactor-type nuclear fuels also use graphite as a carrier, and fuel particles are distributed in a graphite matrix, namely, the graphite is used as a matrix material of the nuclear fuels, such as fuel elements used in high-temperature gas cooled reactors and partial molten salt reactors.

The high temperature gas cooled reactor is mainly divided into a spherical bed reactor and a columnar reactor due to different reactor core structures, and the used fuel element structures are spherical pellets and columnar pellets respectively. The spherical fuel element is composed of an inner fuel area and a fuel-free area outer shell. The fuel area is a sphere formed by dispersing coated fuel particles in a graphite matrix; the fuel-free zone is a spherical shell of the same graphite matrix material surrounding the fuel zone. The fuel and fuel-free zones do not have physical interfaces and their matrix materials are the same, with the graphite matrix material of the spherical fuel elements making up more than 90% of the volume of the fuel elements. The columnar pellets are fuel evenly dispersed in a graphite matrix, and the graphite matrix material accounts for more than 50% of the volume of the element. The manufacturing process of the nuclear fuel adopts powder compression molding technology, and is basically prepared by uniformly mixing matrix graphite powder and cladding particles containing the nuclear fuel, then carrying out compression molding, and then carrying out turning molding, carbonization and purification treatment.

The performance of the matrix material is determined by the preparation process of the matrix raw material to a great extent, the raw material of the graphite matrix is matrix graphite powder, and the preparation of the matrix graphite powder is a very important link in the production of the whole graphite matrix material. The raw materials of the graphite matrix powder are generally graphite powder and a binder. The matrix graphite powder used by nuclear fuel elements is prepared by a wet method from the last 60 years to the present, and is generally prepared by mixing natural graphite powder, artificial stone ink powder and phenolic resin solution dissolved in alcohol into paste, repeatedly kneading and stirring to enable liquid resin to coat the surface of the graphite powder, then granulating the paste, evaporating the alcohol solvent through vacuum drying, and finally crushing on a crusher to obtain the matrix graphite powder. The powder obtained by the matrix graphite powder preparation process has good uniformity, good pressing performance and good final product performance, but the whole process is operated by a wet method, and has the disadvantages of multiple steps and long time consumption.

The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Disclosure of Invention

Object of the Invention

In order to solve the technical problems, the invention aims to provide nuclear fuel matrix graphite powder, a nuclear fuel graphite matrix material and a preparation method. The preparation method of the nuclear fuel matrix graphite powder provided by the invention uses a mechanical fusion method to prepare the matrix graphite powder in the field for the first time, uses natural graphite powder, artificial stone toner and solid binder as raw materials, is a dry process, breaks through the current situation that the matrix graphite powder only has a wet preparation process in the field, does not need to introduce a solvent, shortens the single-batch preparation time from 30-50h of the existing wet process to 1-2h, greatly improves the preparation efficiency, and consumes only 1/40-1/20 of the existing wet process; and can obtain the similar cladding effect of the traditional wet process; meanwhile, the used equipment is more simplified; the shortening of the flow and the simplification of the equipment also effectively reduce the production cost; the dry process avoids the use of flammable and explosive alcohol reagents, and is safer to operate and more environment-friendly. The economic benefit and the social benefit are obvious.

Solution scheme

To achieve the object of the present invention, an embodiment of the present invention provides a preparation method of a nuclear fuel matrix graphite powder, including the following steps:

mixing natural graphite powder, artificial stone ink powder and a solid adhesive; adding the mixture into fusion equipment for treatment; the fusion equipment is used for providing compressive stress and shearing force for the powder, and the binder is coated on the surface of the graphite powder. The binder is in solid form during the preparation process of the invention, whereas the binder is dissolved in solution in the prior wet process. The graphite powder and the binder collide with each other under the energy provided by the fusion equipment, and the local part is heated; under the action of compressive stress, the binder becomes soft, crushed and deformed, and can be mutually embedded with the irregular structure part or the crack of the graphite powder; the shear forces exert a flattening force on the softened binder, thereby causing the binder to surround the graphite particles to form an interfused coating structure.

In one possible implementation manner, the fusion equipment comprises one or more of a mechanical fusion machine, a stirring ball mill or a planetary ball mill; optionally a mechanical fusion machine. Different types of fusion equipment have different fusion effects due to different structures and principles, and different fusion equipment can be selected according to specific requirements during actual use. For mechanical fusion machines, mechanical fusion is achieved by means of special interaction between an internal rotor rotating at high speed and a cylinder; the powder is thrown to the inner wall of the pipe by centrifugal force under the drive of a rotating rotor; a gap is formed between the rotor and the inner wall of the cylinder, and when powder passes through the gap, the rotor moving at a high speed and the inner wall of the cylinder move relatively to generate high shearing force and strong compressive stress on the powder.

In a possible implementation mode of the preparation method, when the fusion equipment is used for processing, the temperature in the container is 40-80 ℃, the relative rotating speed of the rotor and the cylinder is 2000-6000rpm, and the processing time is more than or equal to 5 min.

In a possible implementation manner of the preparation method, the ratio of the particle size D50 of the graphite powder to the particle size D50 of the solid binder is more than or equal to 5: 1. d50 refers to the particle size corresponding to the cumulative percent particle size distribution of a sample at 50%.

In one possible implementation mode of the preparation method, the D50 of the natural graphite powder is 20-60 mu m; d50 of the artificial graphite powder is 25-70 μm; the D50 of the solid binder is less than or equal to 5 mu m.

In one possible implementation manner, the preparation method comprises the following steps: simultaneously adding natural graphite powder, artificial graphite powder and a solid binder into powder mixing equipment, and mixing; then adding the mixture into fusion equipment for treatment to obtain the composite material;

optionally, the mass ratio of the natural graphite powder to the artificial graphite powder is (2-8): 1, the mass ratio of the total weight of the natural graphite powder and the artificial graphite powder to the solid binder is (2-6): 1.

in one possible implementation manner, the preparation method comprises the following steps:

mixing natural graphite powder and a solid binder in powder mixing equipment, and adding the mixture into fusion equipment for treatment to obtain a first fusion; mixing artificial graphite powder and a solid binder in powder mixing equipment, and adding the mixture into fusion equipment for treatment to obtain a second fusion; adding the first fusion and the second fusion into a powder mixing device at the same time, and mixing to obtain the composite material;

optionally, the mass ratio of the natural graphite powder to the solid binder is (2-6): 1; the mass ratio of the artificial graphite powder to the solid binder is (2-6): 1; when the fusion powder is added into a powder mixing device, the mass ratio of the first fusion to the second fusion is (2-8): 1.

in one possible implementation manner of the preparation method, the natural graphite powder comprises one or more of natural crystalline flake graphite or natural microcrystalline graphite; optionally natural flake graphite.

In one possible implementation manner of the preparation method, the artificial graphite powder comprises one or more of graphite powder prepared by taking petroleum coke or pitch coke as a raw material.

In one possible implementation of the above preparation method, the solid binder comprises one or more of phenolic resin, cured furan resin, polyvinyl butyral, epoxy resin, polyurethane resin, carbonaceous solid pitch, mesophase pitch, or self-sintered mesophase carbon microspheres.

In one possible implementation mode of the preparation method, the softening point of the phenolic resin is 100-150 ℃, and the carbon residue rate is 40-70%.

In one possible implementation mode of the preparation method, the softening point of the carbonaceous solid asphalt or the intermediate phase asphalt is 110-300 ℃, and the carbon residue rate is 50-80%.

The embodiment of the invention also provides the nuclear fuel matrix graphite powder prepared by the preparation method of the nuclear fuel matrix graphite powder.

The embodiment of the invention also provides a preparation method of the nuclear fuel graphite base material, which comprises the following steps:

and (3) pressing, carbonizing and purifying the nuclear fuel matrix graphite powder at high temperature to obtain the nuclear fuel graphite matrix material.

In one possible implementation manner, the pressing pressure is 200-; the carbonization is carried out under the protection of inert gas, and the carbonization temperature is 700-1100 ℃; the high-temperature purification temperature is 1600-2500 ℃.

The embodiment of the invention also provides the nuclear fuel graphite base material prepared by the preparation method of the nuclear fuel graphite base material.

Advantageous effects

(1) The preparation method of the nuclear fuel matrix graphite powder provided by the embodiment of the invention is characterized in that the matrix graphite powder is prepared by using a mechanical fusion method in the field for the first time, natural graphite powder, artificial stone toner and a solid binder are used as raw materials, the preparation method is a dry process, the current situation that the matrix graphite powder only has a wet preparation process in the field is broken, no solvent is required to be introduced, the single-batch preparation time is shortened to 1-2h from 30-50h of the existing wet process, the preparation efficiency is greatly improved, and the energy consumption is only 1/40-1/20 of the existing wet process; and can obtain the similar cladding effect of the traditional wet process; meanwhile, the used equipment is more simplified; the shortening of the flow and the simplification of the equipment also effectively reduce the production cost; the dry process avoids the use of flammable and explosive alcohol reagents, and is safer to operate and more environment-friendly. The invention has remarkable economic benefit and social benefit.

(2) The preparation method of the nuclear fuel matrix graphite powder provided by the embodiment of the invention further selects the temperature in the fusion equipment, the relative rotating speed of the rotor and the cylinder and the processing time, and the fusion equipment generates strong pressure stress and shearing force to provide more appropriate energy for a fusion object. The solid adhesive is a brittle material at normal temperature, and under the action of proper energy, the adhesive is softened and can be better embedded, flattened and coated with softer graphite powder. If the energy is too low, the fusion coating effect is not good; if the energy is too high, it may cause intense friction between the powders, heat may locally accumulate for a long time, and the temperature in the container may increase, thereby liquefying the binder to cause a phenomenon of sticking and caking each other.

(3) The preparation method of the nuclear fuel matrix graphite powder provided by the embodiment of the invention further selects the particle sizes of the three raw materials, so that the adhesive can be better coated on the outer surfaces of the graphite particles during mechanical fusion. The coating process is generally to coat the soft and easily deformable material on the surface of the powder with higher hardness. In the invention, the graphite powder has a lubricating effect and is soft in texture; the binder is typically a brittle material at ambient temperature; therefore, the particle sizes of the three raw materials need to be controlled so as to coat the binder on the graphite surface better: the graphite powder is used as an acceptor, the particle size of the graphite powder is far larger than that of a binder used as an object, and the D50 ratio of the particle size of the graphite powder to that of the solid binder is more than or equal to 5: the effect is better at 1.

In addition, the particle size of the graphite powder in a proper range can make the specific surface area, the apparent density, the required amount of the binder and the like more proper, and the obtained matrix graphite powder has better pressing performance and the performance of a final product. The ultrafine graphite powder has large specific surface area and large required binder amount, and when the binder content is too large, the prepared matrix material has high non-graphitized carbon content and is unfavorable for the irradiation resistance in the nuclear fuel element stack; the coarse graphite powder can cause large pores in green bodies of pressed components, so that the density of the matrix material is difficult to ensure, and the mechanical property of the matrix material is also influenced.

Furthermore, the proportion relationship between the graphite powder and the binder is designed according to the particle size, so that the mechanical property of the matrix material can be ensured by fully coating, the graphitization degree of the matrix material can be ensured, and the irradiation resistance in the reactor can be ensured.

(4) The preparation method of the nuclear fuel graphite matrix material provided by the embodiment of the invention has wide application, can be used for preparing matrixes of fuel elements of different reactor types, including high-temperature reactor pebble bed reactors, columnar reactors, molten salt reactors, pressurized water reactors, fast reactors, space reactors and the like, and can also be used for preparing cladding materials of nuclear fuel.

Drawings

One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.

FIG. 1 is a process flow diagram used in examples 1 and 3 of the present invention.

Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the matrix graphite powder prepared by the preparation method provided in example 1 of the present invention.

FIG. 3 is a process flow diagram used in example 2 of the present invention.

FIG. 4 is a process flow diagram used in the comparative example.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.

Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.

Example 1

1. A preparation method of nuclear fuel matrix graphite powder, the technological process is shown in figure 1, and the preparation method comprises the following steps:

mechanically pulverizing natural crystalline flake graphite powder (ash content is 26ppm, graphitization degree is 96, D50 is 78.22 μm) to D50 is 32.84 μm; artificial graphite powder (ash content 12ppm, graphitization degree 88, D50 163.56 μm) is crushed to D50 of 47.74 μm;

phenolic resin is used as a binder, the average molecular weight of the phenolic resin is 1050, the softening point of the phenolic resin is 110 ℃, the carbon residue rate is 51 percent, and the ash content is 32 ppm; the phenolic resin was comminuted to a D50 of 4.3 μm.

The instrument used for testing the particle sizes of the graphite powder and the phenolic resin powder is a Bettersize2000B laser particle size analyzer.

Uniformly mixing the natural graphite powder, the artificial stone powdered ink and the phenolic resin in powder three-dimensional mixing equipment for 30 min; wherein the weight ratio of the natural graphite powder to the artificial graphite powder is 4:1, and the weight ratio of the total weight of the two graphite powders to the phenolic resin is 4: 1;

placing the obtained mixture into a mechanical fusion machine for treatment; in the treatment process, the temperature in the container is 56 ℃, the relative rotating speed of the rotor and the cylinder is 3500rpm, and the treatment time is 30 min; and obtaining matrix graphite powder after the cladding and fusion are finished.

The Scanning Electron Microscope (SEM) picture of the prepared matrix graphite powder is shown in figure 2, and as can be seen from figure 2, no independent phenolic resin particles are seen in the system, and a relatively complete and uniform coating layer is formed on the surface of the graphite powder; the method lays a good foundation for the structure of the interweaving structure formed in the subsequent pressing process and after carbonization, and is also a premise for ensuring the thermodynamic performance of the final matrix material.

2. A method of preparing a nuclear fuel graphite base material, the method comprising the steps of:

and (2) carrying out isostatic pressing on the matrix graphite powder through a soft die, pressing the matrix graphite powder into a ball blank under the pressure of 280MPa, then placing the sample in a carbonization furnace, heating the sample to 800 ℃ under the nitrogen atmosphere, and then heating the sample to 1950 ℃ under the vacuum condition for purification treatment to obtain a graphite matrix material sample.

Example 2

1. A preparation method of nuclear fuel matrix graphite powder, the technological process is shown in figure 3, and the preparation method comprises the following steps:

the natural graphite powder, the artificial stone ink powder and the phenolic resin powder which are crushed in the embodiment 1 are used as raw materials;

uniformly mixing the natural graphite powder and the phenolic resin in a weight ratio of 4:1 for 30min in powder three-dimensional mixing equipment; placing the obtained mixture into mechanical fusion equipment for treatment; in the treatment process, the temperature in the container is 56 ℃, the relative rotating speed of the rotor and the cylinder is 3500rpm, and the treatment time is 30min, so as to obtain a first fusion.

The artificial graphite powder and the phenolic resin are uniformly mixed for 30min in a powder three-dimensional mixing device according to the weight ratio of 4: 1. And then placing the obtained mixture into a mechanical fusion device, wherein the temperature in a container is 56 ℃, the relative rotating speed of a rotor and a cylinder is 3500rpm, and the processing time is 30min during the mixing process to obtain a second fusion.

Uniformly mixing the first fusion and the second fusion in a powder three-dimensional mixing device for 30min at a weight ratio of 4: 1; and obtaining matrix graphite powder after the cladding and fusion are finished.

2. A method of preparing a nuclear fuel graphite base material, the method comprising the steps of:

and (2) carrying out isostatic pressing on the matrix graphite powder through a soft die, pressing the matrix graphite powder into a ball blank under the pressure of 280MPa, then placing the sample in a carbonization furnace, heating the sample to 800 ℃ under the nitrogen atmosphere, and then heating the sample to 1950 ℃ under the vacuum condition for purification treatment to obtain a graphite matrix material sample.

Example 3

1. A preparation method of nuclear fuel matrix graphite powder, the technological process is shown in figure 1, and the preparation method comprises the following steps:

the natural graphite powder and the artificial graphite powder crushed in the embodiment 1 are used as raw materials;

adopts mesophase pitch (prepared by polymerizing petroleum pitch as raw material, the mesophase content is 50%) as a binder, the softening point is 246 ℃, and the carbon residue rate is 70%; the mesophase pitch was pulverized to D50 of 3.9 μm.

The instrument used for testing the particle sizes of the graphite powder and the mesophase pitch powder is a hundred-type Bettersize2000B laser particle size analyzer.

Uniformly mixing the natural graphite powder, the artificial stone powdered ink and the intermediate phase asphalt in a three-dimensional powder mixing device for 30min, wherein the weight ratio of the natural graphite powder to the artificial graphite powder is 4:1, and the weight ratio of the total weight of the two graphite powders to the intermediate phase asphalt is 4: 1;

placing the obtained mixture into mechanical fusion equipment for treatment; in the treatment process, the temperature in the container is 80 ℃, the relative rotating speed of the rotor and the cylinder is 3500rpm, and the treatment time is 30 min; and obtaining matrix graphite powder after the cladding and fusion are finished.

2. A method of preparing a nuclear fuel graphite base material, the method comprising the steps of:

and (2) carrying out isostatic pressing on the matrix graphite powder through a soft die, pressing the matrix graphite powder into a ball blank under the pressure of 280MPa, then placing the sample in a carbonization furnace, heating the sample to 800 ℃ under the nitrogen atmosphere, and then heating the sample to 1950 ℃ under the vacuum condition for purification treatment to obtain a graphite matrix material sample.

Example 4

1. A preparation method of nuclear fuel matrix graphite powder, the technological process is shown in figure 1, and the preparation method comprises the following steps:

mechanically pulverizing natural crystalline flake graphite powder (ash content is 26ppm, graphitization degree is 96, D50 is 78.22 μm) to D50 is 55.46 μm; artificial graphite powder (ash content 12ppm, graphitization degree 88, D50 163.56 μm) is crushed to D50 of 64.17 μm;

phenolic resin is used as a binder, the average molecular weight of the phenolic resin is 1050, the softening point of the phenolic resin is 110 ℃, the carbon residue rate is 51 percent, and the ash content is 32 ppm; the phenolic resin was comminuted to a D50 of 4.5 μm.

The instrument used for testing the particle sizes of the graphite powder and the phenolic resin powder is a Bettersize2000B laser particle size analyzer.

Uniformly mixing the natural graphite powder, the artificial stone powdered ink and the phenolic resin in powder three-dimensional mixing equipment for 50 min; wherein the weight ratio of the natural graphite powder to the artificial graphite powder is 8:1, and the weight ratio of the total weight of the two graphite powders to the phenolic resin is 6: 1;

placing the obtained mixture into a mechanical fusion machine for treatment; in the treatment process, the temperature in the container is 45 ℃, the relative rotating speed of the rotor and the cylinder is 2500rpm, and the treatment time is 10 min; and obtaining matrix graphite powder after the cladding and fusion are finished.

2. A method of preparing a nuclear fuel graphite base material, the method comprising the steps of:

and (2) carrying out isostatic pressing on the matrix graphite powder through a soft die, pressing the matrix graphite powder into a ball blank under the pressure of 280MPa, then placing the sample in a carbonization furnace, heating the sample to 800 ℃ under the nitrogen atmosphere, and then heating the sample to 1950 ℃ under the vacuum condition for purification treatment to obtain a graphite matrix material sample.

Example 5

1. A preparation method of nuclear fuel matrix graphite powder, the technological process is shown in figure 3, and the preparation method comprises the following steps:

mechanically pulverizing natural crystalline flake graphite powder (ash content is 26ppm, graphitization degree is 96, D50 is 78.22 μm) to D50 is 23.75 μm; artificial graphite powder (ash content 12ppm, graphitization degree 88, D50 163.56 μm) is crushed to D50 of 28.67 μm;

phenolic resin is used as a binder, the average molecular weight of the phenolic resin is 1050, the softening point of the phenolic resin is 110 ℃, the carbon residue rate is 51 percent, and the ash content is 32 ppm; the phenolic resin was comminuted to a D50 of 4.1 μm.

The instrument used for testing the particle sizes of the graphite powder and the phenolic resin powder is a Bettersize2000B laser particle size analyzer.

Uniformly mixing the natural graphite powder and the phenolic resin in a weight ratio of 2.5:1 for 20min in a three-dimensional powder mixing device; placing the obtained mixture into mechanical fusion equipment for treatment; in the treatment process, the temperature in the container is 65 ℃, the relative rotating speed of the rotor and the cylinder is 5500rpm, and the treatment time is 20min, so that the first fusion is obtained.

The artificial graphite powder and the phenolic resin are taken according to the weight ratio of 2.5:1 and are uniformly mixed for 20min in a three-dimensional powder mixing device. The resulting mixture was then placed in a mechanofusion device at a temperature of 65 ℃ in the vessel, a rotor to cylinder relative speed of 5500rpm, and a treatment time of 20min to obtain a second fusion.

Uniformly mixing the first fusion and the second fusion in a powder three-dimensional mixing device for 30min at a weight ratio of 2: 1; and obtaining matrix graphite powder after the cladding and fusion are finished.

2. A method of preparing a nuclear fuel graphite base material, the method comprising the steps of:

and (2) carrying out isostatic pressing on the matrix graphite powder through a soft die, pressing the matrix graphite powder into a ball blank under the pressure of 280MPa, then placing the sample in a carbonization furnace, heating the sample to 800 ℃ under the nitrogen atmosphere, and then heating the sample to 1950 ℃ under the vacuum condition for purification treatment to obtain a graphite matrix material sample.

Comparative examples

1. The matrix graphite powder was prepared in a conventional wet process as shown in fig. 4:

the natural graphite powder, the artificial stone ink powder and the phenolic resin powder which are crushed in the embodiment 1 are used as raw materials;

mixing natural graphite powder and artificial graphite powder in a weight ratio of 4:1 mixing in a conical mixer for 30 min;

dissolving phenolic resin (1/4 of the total weight of two graphite powders) in ethanol, wherein the mass percent concentration of the phenolic resin is 35%;

mixing the natural graphite powder, the artificial stone powdered ink and the ethanol solution of the phenolic resin in kneading equipment for 18 hours to form paste; and then granulating the paste by adopting an extrusion granulator, carrying out vacuum drying in a vacuum drier for 10h to evaporate the alcohol solvent, and finally crushing on a crusher to obtain matrix graphite powder.

2. Preparing a graphite base material:

and (2) carrying out isostatic pressing on the matrix graphite powder through a soft die, pressing the matrix graphite powder into a ball blank under the pressure of 280MPa, then placing the sample in a carbonization furnace, heating the sample to 800 ℃ under the nitrogen atmosphere, and then heating the sample to 1950 ℃ under the vacuum condition for purification treatment to obtain a graphite matrix material sample.

Energy production, energy consumption, performance comparison

The main properties of the matrix graphite powders and graphite matrix materials prepared in examples 1 to 3 and comparative examples were tested and compared, and the results are shown in table 1, where table 1 shows the time and energy consumption for preparing the matrix graphite powders and the corresponding key thermodynamic properties of the graphite matrix materials in different examples.

Wherein the crushing strength of the graphite matrix is measured on a universal material tester QT-1136 of ZWICK company in Germany.

The heat conductivity of the graphite matrix is carried out on a JG-71 type laser pulse thermal conductivity meter.

The falling ball strength of the graphite matrix refers to the times that graphite balls freely fall into a simulated ball bed from 4m high altitude repeatedly to generate surface cracking or peeling, and the test is carried out on special falling ball equipment.

Table 1 comparison of process and material properties for the examples

Item	Example 1	Example 2	Example 3	Comparative examples	Technical index
						Time spent in milling	1	2	1	35	/
Energy consumption/kW.h for milling	2.5	5	2.5	～100	/
						Crush strength/kN	21.5	22.4	20.8	22.5	≥18
Thermal conductivity/(W.m-1. K-1)	30.6	30.7	32.9	31.7	≥25
						Density/(g cm-3)	1.74	1.75	1.76	1.75	＞1.70
Ball drop strength/time	＞60	＞60	＞60	＞60	≥50

As can be seen from Table 1, the key performance parameters of the base materials prepared in examples 1-3 can satisfy the requirements of technical indexes, and compared with the comparative examples, the performance is comparable.

From the aspects of time consumption and energy consumption: the traditional wet process has the total time of 35 hours (the time for kneading and vacuum drying is more than 10 hours), and the energy consumption is high. The method not only relates to the pulverization and mixing of powder, but also relates to the processes of heating and dissolving of resin, long-time kneading, extrusion molding, vacuum heating and drying and the like, and uses various devices (kneading devices, vacuum drying devices and the like) with high energy consumption.

In the dry preparation process of the embodiment of the invention, single-batch production only needs 1-2 hours, and the energy consumption is relatively greatly reduced. The used equipment is few, and the used equipment is mainly mechanical motion, and the total power of the equipment is less.

The method only needs 1-2 hours to realize the preparation of matrix graphite powder which needs 35 hours in the traditional process, greatly shortens the preparation time and improves the preparation efficiency. In addition, the method has the advantages of simple equipment, short process time, no need of solvent dissolution and evaporation steps with high energy consumption, and obvious economic benefit, and the energy consumption is only 1/40-1/20 of the traditional process. For the operation of nuclear reactor, the nuclear fuel cost is higher than the operation cost, and the adoption of the process to produce the matrix graphite powder and the fuel elements can reduce the investment of fixed assets such as equipment, factory buildings and the like. The method cancels the use of alcohol solvents, has short flow, can also reduce the labor input, greatly reduces the energy consumption, can obviously reduce the production cost of elements, and has important significance for improving the economical efficiency of various usable reactors.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.